An austenitic stainless steel alloy consisting essentially of, in terms of weight percent ranges 0.15-0.5C; 8-37Ni; 10-25Cr; 2.5-5Al; greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta; up to 3Mo; up to 3Co; up to 1W; up to 3Cu; up to 15Mn; up to 2Si; up to 0.15B; up to 0.05P; up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr; <0.3Ti+V; <0.03N; and, balance Fe, where the weight percent Fe is greater than the weight percent ni, and wherein the alloy forms an external continuous scale comprising alumina, and a stable essentially single phase fcc austenitic matrix microstructure, the austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free. A method of making austenitic stainless steel alloys is also disclosed.
|
12. An austenitic iron base alloy consisting essentially of in weight percent ranges:
0.4C;
23-27Ni;
13-15Cr;
3.0-4Al;
greater than 0.9, up to 1 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 5Mn;
up to 2Si;
0.007-0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weight percent ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase fcc austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
1. An austenitic iron base alloy consisting essentially of, in weight percent ranges:
0.15-0.5C;
8-37Ni;
10-25Cr;
2.5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 15Mn;
up to 2Si;
0.007-0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weight percent ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase fcc austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
14. A method of making iron base alloy articles, comprising the steps of:
providing, in weight percent ranges:
0.15-0.5C;
8-37Ni;
10-25Cr;
2.5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 15Mn;
up to 2Si;
0.007-0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the grou consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weigh percent ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase fcc austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free;
heating said mixture;
cooling said mixture to solidify the mixture to form a solid alloy.
9. The austenitic iron base alloy of
11. The austenitic iron base alloy of
13. The austenitic iron base alloy of
15. The method of
|
This invention was made with government support under DE-AC05-00OR22725 awarded by the United States Department of Energy. The government has certain rights in the invention.
This invention relates generally to alumina forming austenitic (AFA) stainless steels, and more particularly to AFA stainless steels that are useful for casting processes.
Alumina-forming austenitic (AFA) stainless steels are a new class of high-temperature (600-900° C.; 1112-1652° F.) structural alloy steels with a wide range of energy production, chemical/petrochemical, and process industry applications. Examples of such steels can be found in United States patents including U.S. Pat. No. 7,744,813, U.S. Pat. No. 7,754,144, and U.S. Pat. No. 7,754,305, the disclosures of which are incorporated fully by reference. These steels combine the relatively low cost, excellent formability, weldability, and good high-temperature creep strength (resistance to sagging over time) of state-of-the-art advanced austenitic stainless steels with fundamentally superior high-temperature oxidation (corrosion) resistance clue to their ability to form protective aluminum oxide (alumina, Al2O3) surface layers. Conventional high-temperature stainless steels rely on chromium-oxide (chromia, Cr2O3) surface layers for protection from high-temperature oxidation. However, compromised oxidation resistance of chromia in the presence of aggressive species such as water vapor, carbon, sulfur, and the like typically encountered in energy production and process environments necessitates a reduction in operating temperature to achieve component durability targets. This temperature reduction reduces process efficiency and increases environmental emissions.
Alumina grows at a rate 1 to 2 orders of magnitude lower than chromia and is also significantly more thermodynamically stable in oxygen, which results in its fundamentally superior high-temperature oxidation resistance. A further, key advantage of alumina over chromia is its greater stability in the presence of water vapor. Water vapor is encountered in most high-temperature industrial environments, ranging, for example, from gas turbines, combustion, and fossil-fired steam plants to solid oxide fuel cells. With both oxygen and water vapor present, volatile chromium oxy-hydroxide species can form and significantly reduce oxidation lifetime, necessitating significantly lower operating temperatures. This results in reduced process efficiency and increased emissions.
To date AFA alloy development has focused on wrought material forms (plate, sheet, foil, and tubes). However, many applications require complicated component shapes best achieved by casting (engine and turbine components). Casting can also result in lower cost tube production methods for chemical/petrochemical and power generation applications.
An austenitic stainless steel alloy can consist essentially of, in weight percent ranges:
0.15-0.5C;
8-37Ni;
0-25Cr;
2.5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 15Mn;
up to 2Si;
up to 0.05B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and balance Fe.
The weight percent Fe is greater than the weight percent Ni. The alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure. The austenitic matrix is essentially delta-ferrite free and essentially BCC-phase-free.
The C weight percent range can be 0.2-0.5C or 0.2-0.4C. The Cr weight percent range can be 10-15Cr, or 14-16Cr. The Ni weight percent range can be 15-30Ni or 20-30 Ni. The Mn weight percent range can be 0-5Mn. The Ni weight percent range can be 8-12 Ni and the Mn weight percent range can be 5-15. The Si weight percent range can be up to 1Si. The Nb/Ta weight percent range can be greater than 0.9, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta.
An austenitic stainless steel alloy can consist essentially of, in weight percent ranges:
0.2-0.4C;
23-27Ni;
13-15Cr;
3.0-4Al;
greater than 0.9, up to 1 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 5Mn;
up to 2Si;
up to 0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and balance Fe.
The weight percent Fe is greater than the weight percent Ni. The alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure. The austenitic matrix is essentially delta-ferrite free and essentially BCC-phase-free.
In one aspect, the Ni weight percentage can be about 25Ni, the Cr weight percentage can be about 14Cr, the Al weight percentage can be about 3.5Al, and the Nb/Ta weight percentage can be about 0.95 total of at least one element selected from the group consisting of Nb and Ta.
A method of making stainless steel articles, includes the steps of:
providing, in weight percent ranges:
0.15-0.5C;
8-37Ni;
10-25Cr;
2, 5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 15Mn;
up to 2Si;
up to 0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and, balance Fe.
The weight percent Fe is greater than the weight percent Ni. The alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure. The austenitic matrix is essentially delta-ferrite free and essentially BCC-phase-free. The mixture is heated above the melting point. The mixture is cooled to solidify the mixture to form a solid alloy. The heated mixture can be cast prior to cooling.
A fuller understanding of the present invention and the features and benefits thereof will be obtained upon review of the following detailed description together with the accompanying drawings, in which:
Alumina-forming austenitic (AFA) stainless steels are a class of structural steel alloys which comprise aluminum (Al) at a weight percentage sufficient to form protective aluminum oxide (alumina, Al2O3) surface layers. Examples of such steels can be found in United States patents including U.S. Pat. No. 7,744,813, U.S. Pat. No. 7,754,144, and U.S. Pat. No. 7,754,305, the disclosures of which are incorporated fully by reference. The external continuous scale comprising alumina does not form at an Al level below about 2 weight percent. At an Al level higher than about 3 to 5 weight percent, the exact transition dependent on level of austenite stabilizing additions such as Ni (e.g. higher Ni can tolerate more Al), a significant bcc phase is formed in the alloy, which compromises the high temperature properties of the alloy such as creep strength. The external alumina scale is continuous at the alloy/scale interface and though Al2O3 rich the scale can contain some Mn, Cr, Fe and/or other metal additives such that the growth kinetics of the Al rich oxide scale is within the range of that for known alumina scale.
Nitrogen is found in some conventional Cr2O1-forming grades of austenitic alloys up to about 0.5 wt. % to enhance the strength of the alloy. The nitrogen levels in AFA alloys must be kept as low as possible to avoid detrimental reaction with the Al and achieve alloys which display oxidation resistance and high creep strength at high temperatures. Although processing will generally result in some uptake of N in the alloy, it is necessary to keep the level of N at less than about 0.05 wt %, or less than 0.03 wt %, for the inventive alloy. When N is present, the Al forms internal nitrides, which can compromise the formation of the alumina scale needed for the desired oxidation resistance as well as a good creep resistance.
The addition of Ti and/or V is common to virtually all high-temperature austenitic stainless steels and related alloys to obtain high temperature creep strength, via precipitation of carbide and related phases. To permit the formation of the alloys of the invention and the alumina scale, the composition typically has to include little or no titanium or vanadium, with a combined level of less than about 0.3 weight percent. The addition of Ti and V shifts the oxidation behavior (possibly by increasing oxygen permeability) in the alloy such that Al is internally oxidized, requiring much higher levels of Al to form an external Al2O3 scale in the presence of Ti and V. At such high levels, the high temperature strength properties of the resulting alloy are compromised by stabilization of the weak bee Fe phase.
Additions of Nb or Ta are necessary for alumina-scale formation. Too much Nb or Ta will negatively affect creep properties by promoting δ-Fe and brittle second phases.
Within the allowable ranges of elements, particularly those of Al, Cr, Ni, Fe, Mn, Mo and, when present Co, W. and Cu, the levels of the elements are adjusted relative to their respective concentrations to achieve a stable fcc austenite phase matrix. The appropriate relative levels of these elements for a composition is readily determined or checked by comparison with commercially available databases or by computational thermodynamic models with the aid of programs such as Thermo-Calc. In the casting of AFA steels, the partitioning of elements during solidification determines composition control. Non-equilibrium phases formed during solidification will modify the type and amount of strengthening phases.
Additionally, up to 3 weight percent Co, up to 3 weight percent Cu, and up to 1 weight percent W can be present in the alloy as desired to enhance specific properties of the alloy. Rare earth and reactive elements, such as Y, La, Ce, Zr, and the like, at a combined level of up to 1 weight percent can be included in the alloy composition as desired to enhance specific properties of the alloy. Other elements can be present as unavoidable impurities at a combined level of less than 1 weight percent.
The C weight percentage can be 0.15-0.5C. The C weight percentage can be 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.50. The C high/low weight percentage range can be any combination of the above. For example the C weight percentage range can be 0.2-0.5, 0.15-0.4, 0.2-0.4, or 0.3-0.5.
The Ni weight percentage is 8-37Ni. The Ni weight percentage can be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36 or 37Ni, The Ni high/low weight percentage range can be any combination of the above. For example, the Ni weight percentage range can be 8-37, 20-37, 8-12, 20-30, or 23-27 Ni.
The Cr weight percent range can be 10-25Cr. The Cr weight percentage can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25Cr. The Cr high/low Tight percentage range can be any combination of the above. For example, the Cr range can be 10-15, 13-15, or 14-16Cr.
The Al weight percentage range is 2.5-5Al. The Al weight percentage can be 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0. The Al high/low weight percentage range can be any combination of the above. For example, the Al weight percentage range can be 2.5-5, 3-4, or 3-5.
The Nb/Ta weight percentage is greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta. The Nb/Ta weight percentage can be 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5. The Nb/Ta high/low weight percentage range can be any combination of the above. For example, the Nb/Ta weight percentage range can be 0.6-2.5, 0.9-2.5, or 0.9-1.0 Nb/Ta.
The Mo weight percentage is up to 3Mo. The Mo weight percent can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. The Mo high/low weight percentage range can be any combination of the above.
The Co weight percentage is up to 3Co. The Co weight percent can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. The Co high/low weight percentage range can be any combination of the above.
The W weight percentage is up to 1W. The W weight percent can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0. The W high/low weight percentage range can be any combination of the above.
The Cu weight percentage is up to 3Cu. The Cu weight percentage can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. The high/low weight percentage range can be any combination of the above.
The Mn weight percentage is up to 15Mn. The Mn weight percentage can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. The Mn high/low weight percentage range can be any combination of the above. For example, the Mn weight percentage range can be 0-5, 5-15, or 3-7.
Silicon can be added to improve fluidity for casting. The Si weight percentage is up to 2Si. The Si weight percent can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0. The Si high/low weight percentage range can be any combination of the above.
The B weight percentage is up to 0.15B. The B weight percentage can be 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15. The B high/low weight percentage range can be any combination of the above.
The P weight percentage is up to 0.05P. The P weight percentage can be 0, 0.01, 0.02, 0.03, 0.04 or 0.05. The P high/low weight percentage range can be any combination of the above.
The alloys of the invention can comprise up to 1 weight percent total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr. The weight percentage of these elements together can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0. The high/low weight percentage range of these elements can be any combination of the above.
The Ti+V weight percentage is <0.3 Ti+V. The Ti+V weight percentage can be 0.05, 0.10, 0.15, 0.20, 0.25, 0.26, 0.27, 0.28, or 0.29. The Ti+V high/low weight percentage range can be any combination of the above.
The N weight percent range is <0.03N. The N weight percentage can be 0.001, 0.005, 0.010, 0.015, 0.020, 0.025, 0.026, 0.027, 0.028, or 0.029. The N high/low weight percentage range can be any combination of the above.
The balance of the alloy is Fe. The weight percent Fe is greater than the weight percent Ni.
The alloy forms an external continuous scale comprising alumina. The term “continuous” as used herein means that the scale covers at least 75%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 99.9% of the surface area of the alloy.
The alloy is a stable essentially single phase FCC austenitic matrix microstructure. The austenitic matrix is essentially delta-ferrite free and is essentially BCC-phase-free. The term “essentially delta-ferrite free” as used herein can mean that any delta-ferrite present in the alloy comprises less than, by weight, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, or 0.01%, or 0.001% of the alloy. The term “essentially BCC-phase free” as used herein can mean that any BCC-phase present in the alloy comprises less than, by weight, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, or 0.01%, or 0.001% of the alloy.
An austenitic stainless steel alloy according to the invention can consist essentially of, in weight percent ranges:
0.15-0.5C;
8-37Ni;
10-25Cr;
2.5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 15Mn;
up to 2Si;
up to 0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<03 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weight percent Ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
According to another embodiment of the invention, an austenitic stainless steel alloy consists essentially of, in weight percent ranges:
0.2-0.5C;
20-30Ni;
10-15Cr;
2.5-5Al;
greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 5Mn;
up to 1Si;
up to 0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weight percent Ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
According to yet another embodiment of the invention, an austenitic stainless steel alloy consists essentially of, in weight percent ranges:
0.2-0.4C;
23-27Ni;
13-1.5Cr;
3.0-4Al;
greater than 0.9, up to 1 total of at least one element selected from the group consisting of Nb and Ta;
up to 3Mo;
up to 3Co;
up to 1W;
up to 3Cu;
up to 5Mn;
up to 2Si;
up to 0.15B;
up to 0.05P;
up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr;
<0.3 Ti+V;
<0.03N; and,
balance Fe, wherein the weight percent Fe is greater than the weight percent Ni, and wherein said alloy forms an external continuous scale comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure, said austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
The Ni weight percentage in another embodiment is about 2.5Ni, the Cr weight percentage is about 14Cr, the Al weight percentage is about 3.5Al, and the Nb/Ta weight percentage is about 0.95.
A method for casting stainless steel articles is performed by providing a mixture of 0.15-0.5C; 8-37Ni; 10-25Cr; 2.5-5Al; greater than 0.6, up to 2.5 total of at least one element selected from the group consisting of Nb and Ta; up to 3Mo; up to 3Co; up to 1W; up to 3Cu; up to 15Mn; up to 2Si; up to 0.15B; up to 0.05P; up to 1 total of at least one element selected from the group consisting of Y, La, Ce, Hf, and Zr; <0.3 Ti+V; <0.03N; and, balance Fe, wherein the weight percent Fe is greater than the weight percent Ni.
The mixture is heated to above its melting point, typically greater than 1250-1300° C. dependent on exact composition. The molten alloy is then cast, either under vacuum or open to air or an inert cover gas such as Argon. The alloy forms an external continuous scale when exposd to oxidizing conditions from about 500-1000° C., typically 600-900° C. target use temperature comprising alumina, and a stable essentially single phase FCC austenitic matrix microstructure, the austenitic matrix being essentially delta-ferrite free and essentially BCC-phase-free.
Initial experiments were performed on specimens from vacuum arc cast material. Creep tests were conducted at 750° C., 100 MPa. Oxidation resistance was evaluated at 800° C., 10 vol. % water vapor. Predictions of phase equilibria and Scheil simulations were performed using J-Mat Pro 4.1 with a Ni—Fe database.
For service in the temperature range 650° C.-800° C., superior oxidation resistance was associated with an alloy containing larger Nb content in the as-solidified matrix and with aluminum content greater than 2.5 wt. %.
A study of a baseline AFA alloy (AFA 17 in Table 1 (
Table 2 (
The creep and oxidation resistance of as-cast CAFA 1 and CAFA 4 show the benefit of higher levels of C, and delineate a new composition range of unexpectedly good properties for as-cast AFA alloys. These compositions used very high levels of C, either 0.2 or 0.3 wt. % C, based on the unexpected finding of enhanced oxidation resistance with increased C levels. Particularly at higher temperatures, 750° C. and 800° C. CAFA1 (0.2C) and CAFA 4 (0.3C) also showed outstanding creep with increased C content. For example, with CAFA 4 the creep rupture lifetime at 800° C. and 70 MPa is twice that for the high Ni commercial alloy 120, with Fe-37Ni-25Cr base. A higher Ni content equates to greater alloy cost. This improvement in creep was achieved while still maintaining good oxidation resistance (
The CAFA 2, which is CAFA 1 with increased Si from 1 to 2 wt. %, and CAFA 3, which is CAFA 1 with increased Nb from 0.95 to 2.5 wt. %, resulted in a significant degradation in creep rupture life compared to CAFA 1 (
A limiting factor for AFA alloys is sensitivity to nitrogen impurity levels, due to formation of coarse AlN particles which can degrade creep and oxidation resistance. Vacuum arc-casting yields low levels of O and N impurities, typically less than 0.001 to 0.005 wt. %. However, to achieve low cost manufacturing, for some application casting in air rather than vacuum may be preferred.
Creep rupture data for air cast CAFA 1 (
Higher Si and higher Nb content hurt creep in CAFA 2 and 3 (
Tolerance to nitrogen can be achieved by addition of more nitrogen active alloy additions than Al. Based on thermodynamic assessment, Hf. Ti, and Zr can be used to selectively getter N away from Al. The addition of Hf and Zr generally also offers further benefits for oxidation resistance via the well known reactive element effect, at levels up to 1 wt. %. Higher levels can result in internal oxidation and degraded oxidation resistance. Studies of AFA alloys have indicated degradation in oxidation resistance of AFA alloys with Ti and, especially. V additions or impurities, and has indicated limiting these additions to no more than 0.3 wt. % total. Assuming stoichiometric TiN formation, with 0.3 wt. % Ti up to around 0.07 wt. % N is possible, which is sufficient to manage and tolerate the N impurities encountered in air casting. A complication is that Ti will also react with C (as will Nb). Therefore, some combination of Hf or Zr and Ti is desirable to manage and tolerate N effectively.
It is to be understood that while the invention has been described in conjunction with the preferred specific embodiments thereof, that the foregoing description as well as the examples which follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
Yamamoto, Yukinori, Muralidharan, Govindarajan, Brady, Michael P.
Patent | Priority | Assignee | Title |
10207242, | Dec 16 2014 | ExxonMobil Research and Engineering Company | Alumina forming refinery process tubes with mixing element |
10233521, | Feb 01 2016 | Rolls-Royce plc | Low cobalt hard facing alloy |
10233522, | Feb 01 2016 | Rolls-Royce plc | Low cobalt hard facing alloy |
10351784, | Dec 16 2014 | ExxonMobil Chemical Patents INC | Pyrolysis furnace tubes |
11193190, | Jan 25 2018 | UT-Battelle, LLC | Low-cost cast creep-resistant austenitic stainless steels that form alumina for high temperature oxidation resistance |
11479836, | Jan 29 2021 | UT-Battelle, LLC | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
11746402, | Feb 11 2020 | BLYKALLA REAKTORER STOCKHOLM AB | Martensitic steel |
11808297, | Jan 29 2021 | UT-Battelle, LLC | Fastener joint and associated method for avoiding corrosion of dissimilar material fastener joints |
11866809, | Jan 29 2021 | UT-Battelle, LLC | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
Patent | Priority | Assignee | Title |
3754898, | |||
4086085, | Dec 30 1974 | Austenitic iron alloys | |
7744813, | Jan 04 2007 | UT-Battelle, LLC | Oxidation resistant high creep strength austenitic stainless steel |
7754144, | Jan 04 2007 | UT-Battelle, LLC | High Nb, Ta, and Al creep- and oxidation-resistant austenitic stainless steel |
7754305, | Jan 04 2007 | UT-Battelle, LLC | High Mn austenitic stainless steel |
Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
May 24 2011 | UT-Battelle, LLC | (assignment on the face of the patent) | / | |||
Mar 22 2013 | MURALIDHARAN, GOVINDARAJAN | UT-Battelle, LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030075 | /0160 | |
Mar 22 2013 | YAMAMOTO, YUKINORI | UT-Battelle, LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030075 | /0160 | |
Mar 25 2013 | BRADY, MICHAEL P | UT-Battelle, LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030075 | /0160 | |
Mar 26 2013 | UT-Battelle, LLC | U S DEPARTMENT OF ENERGY | CONFIRMATORY LICENSE SEE DOCUMENT FOR DETAILS | 030336 | /0385 |
Date | Maintenance Fee Events |
Mar 29 2013 | ASPN: Payor Number Assigned. |
Oct 17 2016 | M2551: Payment of Maintenance Fee, 4th Yr, Small Entity. |
Nov 22 2016 | ASPN: Payor Number Assigned. |
Nov 22 2016 | RMPN: Payer Number De-assigned. |
Oct 19 2020 | M2552: Payment of Maintenance Fee, 8th Yr, Small Entity. |
Sep 20 2024 | M2553: Payment of Maintenance Fee, 12th Yr, Small Entity. |
Date | Maintenance Schedule |
Apr 30 2016 | 4 years fee payment window open |
Oct 30 2016 | 6 months grace period start (w surcharge) |
Apr 30 2017 | patent expiry (for year 4) |
Apr 30 2019 | 2 years to revive unintentionally abandoned end. (for year 4) |
Apr 30 2020 | 8 years fee payment window open |
Oct 30 2020 | 6 months grace period start (w surcharge) |
Apr 30 2021 | patent expiry (for year 8) |
Apr 30 2023 | 2 years to revive unintentionally abandoned end. (for year 8) |
Apr 30 2024 | 12 years fee payment window open |
Oct 30 2024 | 6 months grace period start (w surcharge) |
Apr 30 2025 | patent expiry (for year 12) |
Apr 30 2027 | 2 years to revive unintentionally abandoned end. (for year 12) |